Selective photoreduction of nitric oxide to nitrogen by nanostructured TiO2 photocatalysts: role of oxygen vacancies and iron dopant

Conventional TiO(2)-based photocatalysts oxidize NO(x) to nitrate species, which do not spontaneously desorb and therefore deactivate the catalyst. We show that the selectivity of this reaction can be changed by creating a large concentration of oxygen vacancies in TiO(2) nanoparticles through thermal reduction in a reducing atmosphere. This results in the photoreduction of nitric oxide (NO) to N(2) and O(2), species which spontaneously desorb at room temperature. The activity of the photoreduction reaction can be greatly enhanced by doping the TiO(2) nanoparticles with Fe(3+), an acceptor-type dopant that stabilizes the oxygen vacancies. Moreover, the photoinduced reduction of Fe(3+) to Fe(2+) provides a recombination pathway that almost completely suppresses the formation of NO(2) and thus enhances the selectivity of the reaction for N(2) formation. Gas chromatography confirms that N(2) and O(2) are formed in a stoichiometric ratio, and the activity for NO decomposition is found to be limited by the concentration of oxygen vacancies. A series of internally consistent reaction equations are proposed that describe all experimentally observed features of the photocatalytic process. The observed influence of oxygen vacancies on the activity and selectivity of photoinduced reactions may lead to new routes toward the design of highly selective photocatalysts.     

Extracting the Green's function from measurements of the energy flux

Existing methods for Green's function extraction give the Green's function from the correlation of field fluctuations recorded at those points. In this work it is shown that the Green's function for acoustic waves can be retrieved from measurements of the integrated energy flux through a closed surface taken from three experiments where two time-harmonic sources first operate separately, and then simultaneously. This makes it possible to infer the Green's function in acoustics from measurements of the energy flux through an arbitrary closed surface surrounding both sources. The theory is also applicable to quantum mechanics where the Green's function can be retrieved from measurement of the flux of scattered particles through a closed surface.     

Unified Green's function retrieval by cross correlation

It has been shown by many authors that the cross correlation of two recordings of a diffuse wave field at different receivers yields the Green's function between these receivers. Recently the theory has been extended for situations where time-reversal invariance does not hold (e.g., in attenuating media) and where source-receiver reciprocity breaks down (in moving fluids). Here we present a unified theory for Green's function retrieval that captures all these situations and, because of the unified form, readily extends to more complex situations, such as electrokinetic Green's function retrieval in poroelastic or piezoelectric media. The unified theory has a wide range of applications in "remote sensing without a source."     

44-Methylgambierone,a new gambierone analogue isolated from Gambierdiscus australes

A new analogue of gambierone, 44-methylgambierone, was isolated from the benthic dinoflagellate Gambierdiscus australes collected from Raoul Island (Rangitahua/Kermadec Islands). This molecule has been previously reported as maitotoxin-3. The structure of 44-methylgambierone was elucidated using 1D- and 2D-nuclear magnetic resonance spectroscopy and mass spectrometry techniques. The nine-ring polyether backbone (A–I) and functional groups (carbonyl, terminal diol, 1,3-diene and monosulphate) are the same for both compounds with the addition of an olefinic methyl group being the only modification in 44-methylgambierone.     

Capillary nematisation of colloidal rods in confinement

ABSTRACT

We confine a colloidal liquid crystal between parallel plates separated down to several times the rod length. By connecting the system to a reservoir we effectively create a grand canonical system, in which the liquid crystal displays an isotropic phase in the reservoir, but upon strong confinement becomes nematic between the parallel plates. This capillary nematisation transition can be followed down to the single particle level by means of laser scanning confocal microscopy. We compare the experimental findings to density functional theories (DFTs), within the Zwanzig model as well as a more advanced DFT, in which the effect of rod flexibility is taken into account.     

Integration of grating couplers with a compact photonic crystal demultiplexer on an InP membrane

We demonstrate the integration of a 30% efficient grating coupler with a compact photonic crystal wavelength demultiplexer (DeMUX). The DeMUX has seven output channels that are spaced 10 nm apart and is aimed at coarse WDM applications. The integrated devices are realized on a high-index-contrast InP membrane using a simple benzocyclobutene wafer bonding technique. Cross talks of -10 to -12 dB for four channels 20 nm apart are obtained without optimization.     

Large-amplitude, spatially correlated fluctuations in BOLD fMRI signals during extended rest and early sleep stages

A number of recent studies of human brain activity using blood-oxygen-level-dependent (BOLD) fMRI and EEG have reported the presence of spatiotemporal patterns of correlated activity in the absence of external stimuli. Although these patterns have been hypothesized to contain important information about brain architecture, little is known about their origin or about their relationship to active cognitive processes such as conscious awareness and monitoring of the environment. In this study, we have investigated the amplitude and spatiotemporal characteristics of resting-state activity patterns and their dependence on the subjects' alertness. For this purpose, BOLD fMRI was performed at 3.0 T on 12 normal subjects using a visual stimulation protocol, followed by a 27 min rest period, during which subjects were allowed to fall asleep. In subjects who were asleep at the end of the scan, we found (a) a higher amplitude of BOLD signal fluctuation during rest compared with subjects who were awake at the end of the scan; (b) spatially independent patterns of correlated activity that involve all of gray matter, including deep brain nuclei; (c) many patterns that were consistent across subjects; (d) that average percentage levels of fluctuation in visual cortex (VC) and whole brain were higher in subjects who were asleep (up to 1.71% and 1.16%, respectively) than in those who were awake (up to 1.15% and 0.96%) at the end of the scan and were comparable with those levels evoked by intense visual stimulation (up to 1.85% and 0.76% for two subject groups); (e) no confirmation of correlation, positive or negative, between thalamus and VC found in earlier studies. These findings suggest that resting-state activity continues during sleep and does not require active cognitive processes or conscious awareness.     

The role of distonic ions in the formation of CH3NH 3 + and (CH3)2NH 2 + from the molecular ions of octopamine and synephrine

It is shown by mass-analyzed ion kinetic energy spectrometry that the metastably decomposing molecular ions of octopamine (p-HOC₆H₄CH(OH)CH₂NH₂) and synephrine (p-HOC₆H₄CH(OH)CH₂NHCH₃) yield only protonated methylamine and dimethylamine, respectively, as product ions. From deuterium labeling and variation of the internal energy of the molecular ions, experimental support has been obtained that these product ions are generated via the occurrence of a distonic ion-neutral complex. In the case of octopamine, this complex would consist of a nitrogen-protonated aminomethyl radical and p-hydroxylbenzaldehyde in which the former species abstracts the aldehydic or phenolic hydrogen atom from the latter to give protonated dimethylamine.